Synthesis of sterically hindered secondary aminoether alcohols

ABSTRACT

Severely sterically hindered secondary aminoether alcohols are prepared by reacting an organic carboxylic acid or alkali metal salt of an organic carboxylic acid with a sulfonyl halide, a sulfuryl halide, a mixed sulfuryl ester halide or a mixed sulfuryl amide halide to yield a sulfonic-carboxylic anhydride compound which is then reacted with a dioxane to cleave the ring of the dioxane, yielding a cleavage product which cleavage product is then aminated with an alkylamine and hydrolyzed with base to yield the severely sterically hindered secondary aminoether alcohol.

This application is the U.S. National Phase filing of PCT ApplicationNo. PCT/US2005/003052 filed Feb. 1, 2005, which claims priority to U.S.Provisional Patent Application No. 60/545,118 filed Feb. 17, 2004.

FIELD OF THE INVENTION

The present invention relates to a method for the preparation ofseverely sterically hindered secondary aminoether alcohols which areuseful in the removal of hydrogen sulfide from gaseous streamscontaining hydrogen sulfide and which may also contain carbon dioxide.

DESCRIPTION OF RELATED ART

It is well-known in the art to treat gases and liquids, such as mixturescontaining acidic gases including CO₂, H₂S, CS₂, HCN, COS and oxygen andsulfur derivatives of C₁ to C₄ hydrocarbons with amine solutions toremove these acidic gases. The amine usually contacts the acidic gasesand the liquids as an aqueous solution containing the amine in anabsorber tower with the aqueous amine solution contacting the acidicfluid countercurrently. Usually this contacting results in thesimultaneous removal of substantial amounts of both the CO₂ and H₂S.U.S. Pat. No. 4,112,052, for example, utilizes a sterically hinderedamine to obtain nearly complete removal of CO₂ and H₂S acid gases. Thisprocess is particularly suitable for systems in which the partialpressures of the CO₂ and related gases are low. For systems where thepartial pressure of CO₂ is high or where there are many acid gasespresent, e.g., H₂S, COS, CH₃SH, CS₂, etc., a process utilizing an aminein combination with a physical absorbent, referred to as a “non-aqueoussolvent process” is practiced. Such a system is described in U.S. Pat.No. 4,112,051.

Selective removal of H₂S from acid gas systems containing both H₂S andCO₂, however, is very desirable. Such selective removal results in arelatively high H₂S/CO₂ ratio in the separated acid gas whichfacilitates the subsequent conversion of the H₂S to elemental sulfur inthe Claus process.

The typical reactions of aqueous secondary and tertiary amines with CO₂and H₂S can be represented as follows:

where R is the same or different organic radical and may be substitutedwith a hydroxyl group. Because the reactions are reversible they aresensitive to the CO₂ and H₂S partial pressures which is determinative ofthe degree to which the reactions occur.

Selective H₂S removal is particularly desirable in systems having lowH₂S/CO₂ ratios and relatively low H₂S partial pressures as compared tothat of the CO₂. The ability of amine to selectivity remove H₂S in suchsystems is very low.

Solutions of primary and secondary amines such as monoethanolamine(MEA), diethanolainne (DEA), diisopropanolamine (DPA), andhydroxyethoxyethylamine (DEA) absorb both H₂S and CO₂, and thus haveproven unsatisfactory for the selective removal of H₂S to the exclusionof CO₂. The CO₂ forms carbamates with such amines relatively easily.

H₂S has been selectively removed from gases containing H₂S and CO₂ byuse of diisopropanolamine (DIPA) either alone or mixed with anon-aqueous physical solvent such as sulfolane. Contact times, however,must be kept short to take advantage of the faster reaction of H₂S withthe amine as compared to the rate of CO₂ reaction with the amine.

Frazier and Kohl, Ind. and Eng. Chem., 42, 2288 (1950) showed that thetertiary amine methydiethanolamine (MDEA) is more selective toward H₂Sabsorption as compared to CO₂. CO₂ reacts relatively slowly withtertiary amines as compared to the rapid reaction of the tertiary aminewith H₂S. However, it has the disadvantage of having a relatively lowH₂S loading capacity and limited ability to reduce the H₂S content tothe desired level at low H₂S pressures encountered in certain gases.

UK Patent Publication No. 2,017,524A discloses the use of aqueoussolutions of dialkylmonoalkanolamines, e.g., diethylmonoethanol amine(DEAE), for the selective removal of H₂S, such material having higherselectivity and capacity for H₂S removal at higher loading levels thanMDEA. DEAE, however, has the disadvantage of a low boiling point of 161°C., making it relatively highly volatile resulting in large materialloss.

U.S. Pat. No. 4,471,138 the entire teaching of which is incorporatedherein by reference, teaches severely sterically hindered acyclicsecondary aminoether alcohols having a high selectivity for H₂S comparedto CO₂. Selectivity is maintained at high H₂S and CO₂ loadings.

The severely sterically hindered acyclic amine ether alcohols of U.S.Pat. No. 4,471,138 are represented by the general formula:

wherein R₁ and R₂ are each independently selected from the groupconsisting of alkyl and hydroxyalkyl radicals having 1-4 carbon atoms,R₃, R₄, R₅ and R₆ are each independently selected from the groupconsisting of hydrogen, alkyl, and hydroxyalkyl radicals having 1-4carbon atoms, with the proviso that at least one of R₄ or R₅ bonded tothe carbon atom which is directly bonded to the nitrogen atom is analkyl or hydroxyalkyl radical when R₃ is hydrogen, x and y are eachpositive integers ranging from 2-4, and z is a positive integer rangingfrom 1-4. These materials are prepared by a high temperature reactionpreferably in the presence of a solvent, of a secondary or tertiaryalkyl primary amine with an ether alcohol containing a carbonylfunctionality in the presence of a source of hydrogen or with ahaloalkoxyalkanol. Preferably the composition is of the general formula:

wherein:

-   R₁=R₂=R₃=CH₃—; R₄=R₅=R₆=H;-   R₁=R₂=R₃=CH₃—; R₄=H or CH₃; R₅=R₆=H;-   R₁=R₂=R₃=R₆=CH₃—; R₄=R₅=H;-   R₁=R₂=R₃=CH₃CH₂—; R₄=R₅=R₆=H; or-   R₁≠R₂≠R₃=H, CH₃—, CH₃CH₂—; R₄≠R₅≠R₆=H, CH₃—;    and where x=2 or 3.

U.S. Pat. No. 4,487,967 is directed to a process for preparing severelysterically hindered secondary aminoether alcohols by reacting a primaryamino compound with a polyalkenyl ether glycol in the presence of ahydrogenation catalyst at elevated temperatures and pressures. Theprimary amino compounds employed have a general formula:R¹—NH₂where R¹ is selected from the group consisting of secondary or tertiaryalkyl radicals having 3 to 8 carbon atoms or cycloalkyl radicals having3 to 8 carbon atoms. The polyalkenyl ether glycols employed have thegeneral formula:

where R₂, R₃, R₄ and R₅ are each independently selected from the groupconsisting of hydrogen, C₁-C₄ alkyl radicals, and C₃-C₈ cycloalkylradicals, with the proviso that if the carbon atom of R₁ directlyattached to the nitrogen atom is secondary, at least one of R₂ and R₃directly bonded to the carbon which is bonded to the hydroxyl group isas alkyl or cycloalkyl radical, x and y are each positive integersindependently ranging from 2 to 4 and z is from 1 to 10, preferably 1 to6, more preferably 1 to 4. The process is carried out in the presence ofa catalytically effective amount of a supported Group VIII metalcontaining hydrogenation catalyst at elevated temperatures and pressureand the mole ratio of amino compound to polyalkenyl ether glycol is lessthan 2:1 when z is greater than 1.

SUMMARY OF THE INVENTION

A new process is disclosed for the production of severely stericallyhindered secondary aminoether alcohols of the general formula 1:

wherein R¹ and R² are each independently selected from the groupconsisting of alkyl and hydroxyalkyl radicals having 1 to 4 carbonatoms, preferably 1 to 2 carbon atoms, or R¹ and R² in combination withthe carbon atom to which they are attached form a cycloalkyl grouphaving 3 to 8 carbons; R³ is selected from the group consisting ofhydrogen, alkyl or hydroxyalkyl radicals having 1 to 4 carbon atoms, andmixtures thereof, preferably 1 to 2 carbon atoms, preferably alkyl orhydroxyalkyl radicals having 1 to 4 carbon atoms, more preferably 1 to 2carbon atoms; R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, and R¹¹ are the same ordifferent and are selected from hydrogen, alkyl or hydroxyalkyl radicalshaving 1 to 4 carbon atoms, preferably 1 to 2 carbon atoms, orcycloalkyl radicals having 3 to 8 carbons; R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰,and R¹¹ are preferably hydrogen provided that when R³ is hydrogen atleast one of R⁴ and R⁵ bonded to the carbon directly bonded to thenitrogen atom is an alkyl or hydroxyalkyl radical. The process involvesreacting an organic carboxylic acid or a salt of a carboxylic acid ofthe formula:

wherein R¹² is selected from the group consisting of alkyl radicalshaving 1 to 4 carbon atoms, preferably 1 to 2 carbon atoms, mostpreferably methyl, aryl radicals, substituted aryl radicals, preferablyphenyl substituted with a hydrogen or one or more alkyl radicals having1-10 carbon atoms, preferably 1-4 carbon atoms, most preferably methylin the para position, and mixtures thereof, and Y is selected from thegroup consisting of hydrogen, alkali metal, ammonium, and mixturesthereof, preferably hydrogen or sodium, with a sulfonyl halide, asulfuryl halide, a mixed sulfuryl ester halide, or a mixed sulfurylamide halide of the formula:R¹⁴SO₂X, SO₂X₂, R¹⁴OSO₂X or R₂ ^(14,14′)NSO₂X   (3)wherein X is selected from the group consisting of F, Cl, Br, I, andmixtures thereof, preferably F, Cl, most preferably Cl, R¹⁴ and R^(14′)are the same or different and each is selected from the group consistingof alkyl radicals having 1 to 4 carbon atoms, preferably 1 to 2 carbonatoms, most preferably methyl, haloalkyl radicals of the formulaC_(n)H_((2n+1)-w)Z_(w) wherein n is 1 to 4 preferably 1 to 2, and mostpreferably 1; Z is selected from the group consisting of F, Cl, Br, I,preferably F and Cl, most preferably F; and w ranges from 1 to 5,preferably 1 to 3, most preferably 3, aryl radicals 4

wherein R¹⁵, R¹⁶, R¹⁷, R¹⁸, and R¹⁹ are the same or different and areselected from hydrogen and alkyl radicals having 1 to 20 carbon atoms,preferably R¹⁵, R¹⁶, R¹⁸, and R¹⁹ are hydrogen and R¹⁷ is selected fromhydrogen and an alkyl radicals having 1-4 carbons, preferably 1 to 2carbons, more preferably methyl, and mixtures thereof, to yieldsulfonic-carboxylic anhydride compounds of the formula 5:

which is then reacted with a dioxane of the formula 6:

wherein R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, and R¹¹ are the same or differentand are selected from hydrogen, alkyl and hydroxyalkyl radicals having 1to 4 carbons, preferably 1 to 2 carbons or cycloalkyl radicals having 3to 8 carbons, more preferably R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, and R¹¹ arehydrogen, to yield cleavage product materials of formula 7

or mixtures thereof. It is not necessary that the product from eachreaction step be isolated before being reacted with the reactant of asubsequent reaction step up to this point. A cleavage product is stillproduced The mixing of the organic carboxylic acid or salt thereof witha sulfonyl halide, sulfuryl halide, mixed sulfuryl ester halide or mixedsulfuryl amide halide and the dioxane can be in any order or sequence.Thus, the organic carboxylic acid or salt thereof can be mixed with thesulfonyl halide, etc. and then mixed with the dioxane, or the dioxanecan be first mixed with the sulfonyl halide, etc. and then the organiccarboxylic acid or salt thereof can be added, or the organic carboxylicacid or salt thereof and the dioxane can be mixed followed by theaddition of the sulfonyl halide, etc. Thus, the combination of theorganic carboxylic acid or salt thereof with the dioxane and thesulfonyl halide, sulfuryl halide, mixed sulfuryl ester halide or mixedsulfuryl amide halide can be combined into a single reaction mixture andreacted as a single mixture in the one step production of the desiredcleavage product. This cleavage product is then reacted with analkylamine of the formula 8:

wherein R¹, R² and R³ are as previously defined to yield 9

which is subsequently hydrolyzed with a base to yield 1

The preferred compounds defined by the general formula above include:

Typical starting materials to use as the first component are:

Other materials of the types described above can be readily envisioned.

This material is then is reacted with second component, typically

Similarly, other materials of the type described above can be readilyenvisioned.

The reaction of two such components yields acyl sulfonates 5a, 5b, 5cand 5d. The reaction can be conducted at a temperature in the range ofbetween about −20 to 200° C., preferably about −20 to 150° C., morepreferably about 0 to 120° C., and a pressure between about 1 bar to 100bars, preferably about 1 bar to 50 bars, more preferably about 1 bar to10 bars.

The reaction can be carried out neat, that is, in the absence of anysolvent provided one or the other of the reactants in a liquid andcapable of dissolving the non-liquid reactant, or both are liquid.Alternatively, an inert added solvent can be used such as sulfolane,hexanes or acetonitrile. Preferably the dioxane for the subsequentcleavage reaction is used as the solvent resulting in all threereactants being present in a unified first step wherein the reactionmixture contains the dioxane, organic carboxylic acid or salt thereofand the sulfonyl halide, sulfuryl halide, mixed sulfuryl ester halide ormixed sulfuryl amide halide. This reaction mixture can then be reactedunder the conditions subsequently described for the dioxane cleavagereaction, yielding the cleavage product described by general formula 4.

The sulfonate 5a and/or 5b are reacted with a 1,4-dioxane, which istypically of the formula:

Other substituted isomers can be readily envisioned. Preferably, the1,4-dioxane is

Reaction at elevated temperature is for a time sufficient to cleave thedioxane ring and to achieve about 60-90% conversion to cleavage product.The dioxane also serves as the solvent for the reaction. The molar ratioof dioxane to sulfonate can range from about 1:1 to about 10:1,preferably about 1:1 to about 8:1, most preferably about 1:1 to about5:1. The reaction can be carried out in the absence of any addedsolvent, e.g., the dioxane serving as the solvent, or an additionalsolvent such as acetonitrile or toluene can be used, the reaction beingconducted at temperatures between about 50° C. to about 200° C.,preferably about 70° C. to about 160° C., more preferably about 80° C.to about 140° C.

Preferably, the reaction is carried out in the absence of any addedsolvent, the dioxane serving as both reactant and solvent, at atemperature in the range of about 50° C. to about 160° C., preferablyabout 70° C. to about 160° C., more preferably about 80° C. to about140° C.

The dioxane cleavage step recited above are described in greater detailby Karger and Mazur in “The Cleavage of Ethers by MixedSulfonic-Carboxylic Anhydrides”, Journal of the American ChemicalSociety, 1968, 90, 3878-3879. See also, “Mixed sulfonic-carboxylicanhydrides. I. Synthesis and thermal stability. New syntheses ofsulfonic anhydrides” Journal of Organic Chemistry, 1971, 36, 528, and“Mixed sulfonic-carboxylic anhydrides. II. Reactions with aliphaticethers and amines” Journal of Organic Chemistry, 1971, 36, 532.

The cleavage product 7a and/or 7b and/or 7c and/or 7d is then aminatedwith an amine 8 typically of the formula:

for a time sufficient to replace the —O—SO₂—R¹⁴ or the sulfonate groupin 7a and/or 7b and/or 7c and/or 7d by the amine 8. In the case of theamination of materials 7a, 7c and 7d, the amine to sulfonate group moleratio is in the range of about 1:1 to about 10:1, preferably about 1:1to about 8:1, more preferably about 1:1 to 4:1, while in the case of theamination of material 7 b the amine to sulfonate group ratio is in therange of about 2:1 to about 10:1, preferably about 2:1 to about 8:1,more preferably about 2:1 to about 4:1. Expressed differently, ingeneral the amine to group being replaced mole ratio can range fromabout stoichiometric to about 10:1, preferably about stoichiometric toabout 8:1, more preferably about stoichiometric to about 4:1.

This amination step can be carried out under any conditions typical inthe art. Amination can be conducted at atmospheric or at elevatedpressure, elevated pressure being especially suitable when amination isperformed using relatively low boiling amines such as t-butyl amine.

The amination can be conducted at pressures of from about atmospheric (1bar) to about 100 bars, preferably about 1 to about 50 bars, and attemperatures of from about 40° C. to about 200° C., preferably about 40°C. to about 125° C. The amination can be performed using reflux, butthis is not absolutely necessary. An inert solvent can be optionallyused, such as benzene, toluene, diethyl ether, hexane, and the like.

Finally, the resultant 9

is hydrolyzed using a base to yield the final desired product 1. Typicalbases include an alkali metal hydroxide, an alkali metal carbonate, oran alkali metal alkoxide, such as sodium hydroxide, sodium carbonate,sodium methoxide, sodium tert-butoxide, etc. Reaction is conducted atfrom about 20° C. to about 110° C., preferably about 20° C. to about 50°C. Reaction under reflux is effective and a desirable technique.

Use of a solvent is optional for the hydrolysis reaction, one being usedif the reactants are not already in the liquid form. Solvents caninclude water, or alcohol and mixtures thereof.

If alcohols are used, they can be of the same carbon number or are thesame alcohols from which the alkoxide bases themselves are derived.Thus, methanol would be a suitable solvent to use where the base is analkali methoxide.

EXAMPLES Cleavage with Methyl Acetyl Sulfate Generated in situ usingMethyl Chlorosulfonate and Acetic Acid in the Presence of Triethylamine

Methyl chlorosulfonate was prepared according to known procedure[Heller, M. S.; Lorah, D. P.; Cox, C. P., Chem. Eng. Data, 1983, 27,134] by the reaction of sulfuryl chloride with methanol as follow:Methanol (15 g, 0.47 mol) was added dropwise to sulfuryl chloride at 0°C. (ice-bath cooling) and the reaction mixture was stirred at 0° C. for3 hours. After evolution of hydrogen chloride ceased, the reactionmixture was distilled under reduced pressure to give methylchlorosulfonate (23.5 g, 38%, bp 62° C./52-53 mm Hg; lit.[Heller, M. S.;Lorah, D. P.; Cox, C. P., Chem. Eng. Data, 1983, 27, 134] 55-56° C./39mm Hg). ¹H NMR (CDCl₃) δ4.21 (s, 3H); ¹³C NMR (CDCl₃) δ61.2

Cleavage of dioxane. A 25 mL one-necked flask was charged with aceticacid (0.97 mL, 1.0 g, 16.7 mmol), dioxane (7 mL, 7.0 g, 80 mmol), methylchlorosulfonate (2.0 g, 15.3 mmol) and then with triethylamine (2.153mL, 1.56 g, 15.3 mmol) at room temperature under nitrogen. The reactionmixture was refluxed for 72 h. The reaction progress was monitored byNMR. The reaction mixture was then evaporated under vacuum. Dry toluene(15 mL) and tert-butylamine (8.4 mL, 5.85 g, 80 mmol) were added to theresidue and the mixture was gently refluxed for 24 hours. The reactionmixture was then cooled to room temperature and filtered. The solid waswashed with toluene. The combined filtrate was evaporated under vacuum.The residue was extracted with toluene; the extract was filtered andevaporated under vacuum to give 0.3 g of brown oil. The NMR test showedthe trace presence of desired product (t-BuNHCH₂CH₂OCH₂CH₂OAc). Thesignals in ¹H NMR spectrum suggest the presence of acetates(HOCH₂CH₂OCH₂CH₂OAc) and/or (AcOCH₂CH₂OCH₂CH₂OAc).

1. A method for the synthesis of severely sterically hindered secondaryaminoether alcohols of the formula

wherein R¹ and R² are each selected from the group consisting of alkyl,hydroxylalkyl radicals having 1 to 4 carbon atoms or in combination withthe carbon atom to which they are attached they form a cycloalkyl grouphaving 3 to 8 carbon atoms, and R³ is selected from the group consistingof hydrogen, alkyl, hydroxyalkyl radicals having 1 to 4 carbon atoms,and mixtures thereof, and R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰ and R¹¹ are thesame or different and are selected from the group consisting ofhydrogen, alkyl and hydroxyalkyl radicals having 1 to 4 carbons providedthat at least one of R⁴ or R⁵ bonded to the carbon atom directly bondedto the nitrogen atom is an alkyl or hydroxyalkyl radical when R³ ishydrogen, the process involving reacting an organic carboxylic acid orsalt of a carboxylic acid of the formula

wherein R¹² is selected from the group consisting of alkyl radicalshaving 1 to 4 carbon atoms, aryl radicals bearing hydrogen or one ormore C₁-C₁₀ alkyl groups substituted thereon, and mixtures thereof, andY is selected from the group consisting of hydrogen, alkali metal,ammonium, and mixtures thereof, with a sulfonyl halide, a sulfurylhalide, a mixed sulfuryl ester halide, or a mixed sulfuryl amide halideof the formulaR¹⁴SO₂X, SO₂X₂, R¹⁴OSO₂X, or R₂ ^(14,14′NSO) ₂X wherein X is selectedfrom the group consisting of F, Cl, Br, I, and mixtures thereof, and R¹⁴and R^(14′) are the same or different and each is selected from thegroup consisting of alkyl radicals having 1 to 4 carbon atoms, haloalkylradicals of the formula C_(n)H_((2n+1)−w)Z_(W) wherein n is 1 to 4, Z isselected from the group consisting of F, Cl, Br, I, and mixturesthereof, and w ranges from 1 to 5, and aryl radicals

wherein R¹⁵, R¹⁶, R¹⁷, R¹⁸, and R¹⁹ are the same or different and areselected from hydrogen and alkyl radicals having 1 to 20 carbon atoms,and mixtures thereof, to yield acyl sulfonate material of the generalformula

which is then reacted with a dioxane of the formula

wherein R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, and R¹¹ are the same or differentand are selected from hydrogen, alkyl and hydroxyalkyl radicals having 1to 4 carbons to yield

which is then aminated with an alkylamine of the formula

wherein R¹, R², and R³ are as previously defined to yield

which is then hydrolyzed with base to yield


2. The method of claim 1 for the synthesis of severely stericallyhindered secondary aminoether alcohols using sulfonyl halide of theformula R¹⁴SO₂X.
 3. The method of claim 1 for the synthesis of severelysterically hindered secondary aminoether alcohols using sulfuryl halideof the formula SO₂X₂.
 4. The method of claim 1 for the synthesis ofseverely sterically hindered secondary aminoether alcohols using themixed sulfuryl ester halide of the formula R¹⁴OSO₂X.
 5. The method ofclaim 1 for the synthesis of severely sterically hindered secondaryaminoether alcohols using the mixed sulfuryl amide halide of the formulaR₂ ^(14,14′)NSO₂X.
 6. The method according to claim 1, 2, 3, 4 or 5wherein R¹, R² and R³ are methyl radicals.
 7. The method according toclaim 1, 2, 3, 4 or 5 wherein R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, and R¹¹ arehydrogen.
 8. The method according to claim 1, 2, 3, 4 or 5 wherein R¹⁵,R¹⁶, R¹⁸, and R¹⁹ are hydrogen and R¹⁷ is hydrogen or methyl.
 9. Themethod according to claim 1, 2, 3, 4 or 5 wherein the base is selectedfrom alkali metal hydroxide, alkali metal alkoxide, or alkali metalcarbonate.
 10. The method according to claim 1, 2, 3, 4 or 5 wherein Yis hydrogen or sodium.
 11. The method according to claim 1, 2, 3, 4 or 5wherein R¹, R² and R³ are methyl, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, and arehydrogen, R¹⁵, R¹⁶, R¹⁸, and R¹⁹ are hydrogen, R¹⁷ is hydrogen ormethyl, and Y is hydrogen, sodium, or ammonium.
 12. The method accordingto claim 1, 2, 3, 4 or 5 wherein the acyl sulfonate is made by reactingorganic carboxylic acid or the salt of a carboxylic acid with thesulfonyl halide, sulfuryl halide, mixed sulfuryl ester halide or mixedsulfuryl amide halide at a temperature in the range of between about −20to 200° C. at a pressure between about 1 bar and 100 bars, the acylsulfonate is reacted with the dioxane at a molar ratio of dioxane toacyl sulfonate in the range of 1:1 to 10:1 at a temperature of betweenabout 50° C. to about 200° C. to yield a cleavage product, the cleavageproduct and the alkyl amine reacted at an amine to sulfonate group ratioranging from about stoichiometric to about 10:1 at pressure of fromabout atmospheric (1 bar) to about 100 bars at temperature of from about40° C. to about 200° C., and the resulting aminated product ishydrolyzed with base at a temperature from about 20° C. to about 110° C.13. The method according to claim 1, 2, 3, 4 or 5 wherein the organiccarboxylic acid or the salt thereof, the sulfonyl halide, sulfurylhalide, mixed sulfuryl ester halide or mixed sulfuryl amide halide andthe dioxane care combined in a single step to produce a reactionmixture, the reaction mixture being heated at a temperature of betweenabout 50° C. to about 200° C. to produce the cleavage product, thecleavage product and the alkylamine are reacted at am amine to cleavageproduct ratio ranging from about stoichiometric to about 10:1 at apressure from about atmospheric (1 bar) to about 100 bars at atemperature of from about 40° C. to about 200° C., the resultingaminated product being reacted with base at a temperature from about 20°C. to about 110° C.